Creamy high-foam liquid built detergent composition



United States Patent Ofifice 3,072,578 Patented Jan. 8, 1963 This invention relates to an improved liquid built detergent. More particularly, this invention relates to a stable creamy built high-foam liquid detergent. This invention also relates to a process for the preparation of the liquid detergent.

A good built liquid detergent should contain all of the essential ingredientsof a good, dry built detergent formulation, i.e., a surfactant, a phosphate builder, an anticorrosion agent, and an antiredeposition agent. In addition, a foam stabilizer is sometimes necessary when a high persistentfoam is desirable, and other'ingredients such as optical brighteners, dyes, perfumes etc. may be incorporated where desired. However, it has not been commercially possible heretofore to incorporate these ingredients into a liquid formulation and still obtain a stable liquid detergent. Many formulations prepared heretofore have been physically unstable resulting in separation of the detergent into two or more incompatible layers. This has been a serious detriment to commercialization of built liquid detergents in the past. Recombination of the separated detergent before use is often diflicult, in addition to being a nuisance. Unless the recombination is performed with care it results in the use in each Washing operation of an improperly blended detergent with resultant decrease in the performance of the detergent.

In efforts to overcome the above-mentioned disadvantages, detergent formulators have .heretofore resorted to a number of undesirable devices. Sodium silicate is difficult to incorporate into liquid detergent formulations and one common device is to leave out this essential ingredient or to decrease its concentration to much less than that necessary for proper protection of metal surfaces which come in contact with the liquid detergent. This results in excessive corrosion of metal containers and of metal washing machine parts. Another device is to omit sodium carboxymethyl-cellulose from the formulation resulting in increasing grayness of fabrics laundered with such detergents. Another device is toresort to expensive combinations of specially purified surfactants with unduly large proportions of solubilizers such assodium xylene sulfonate. These latter substances increase the cost of built liquid detergents without contributing appreciably to detergency. More expensive potassium-containing surfactants have also been used in place of the less soluble, less expensive sodium-containing surfactants. It is possible to decrease the cost of these built detergents by decreasing the concentration of the expensive specially purified surfactants but the performance suffers. Another device is to reduce the proportions of the essential ingredients in the liquid formulations, but this results in poorer performance unless proportionately larger amounts of the detergent are used in the washing operation. This results in higher cost to the consumer. Moreover, simple dilution of the liquid detergent does not by .the total water content of our composition. only percent is active, the other 10 percent being sodium sulfate.

itself necessarily permit incorporation of the proper amount of certain ingredients such as sodium silicate and sodium carboxymethylcellulose.

It is an object of this invention to provide a stable highfoam built liquid detergent. It is a further object of this invention to provide a stable liquid detergent which contains all of the essential ingredients of a good, dry detergent formulation. It is another object of this invention to provide a stable liquid detergent employing cheap commercially available materials. Furthermore, it is an object of this invention to provide a process for the preparation of these stable high-foam built liquid detergents.

According to this invention there is provided a stable high-foam built detergent which can be either a pourable liquid or a paste depending upon the concentrations of the ingredients employed. These formulations comprise tetrapotassium pyrophosphate, an alkali metal silicate, a sodium alkyl aryl sulfonate, carboxymethylcellulose, and a mixture of lauryl and myristyl esters containing both primary amino and sulfated groups, and water. if desired, a foam stabilizer such as fatty acid alkanol amides, water soluble dyes and antitarnishing agents for metal surfaces may be included in the formulation.

In the above compositions the pyrophosphate is employed as the phosphate builder and the alkali metal silicate functions as an anticorrosion agent. The sodium alkyl aryl sulfonate is employed as a surfactant, the carboxymethylcellulose as an antiredeposition agent and the mixture of lauryl and myristyl esters is used as a dispersing agent.

It is preferred to add our surfactant .to the formulation as a cheap 35 percent solids content water slurry in which case, the water content of the slurry forms a portion of Of the solids Hereinafter whenever we refer to the weight percent of the surfactants employed it will be understood to refer to the solids content.

Broadly speaking the formulations of this invention may contain from about 13 percent to 30 percent by weight tetrapotassium pyrophosphate, from about 1.4 percent to about 2.3 percent by weight of SiO as sodium silicate in which the ratio of SiO /Na O may vary from about 3.2/1 to about 1/1, about 14 to about 23.6 percent by weight sodium alkyl aryl sulfonate, from about 0.1 to 3 percent by weight carboxymethylcellulose, from about 4.3 to about 10 percent by weight of a mixture of lauryl and myristyl esters containing both primary amino and sulfated groups, with water making up the balance of the formulation.

When a creamy liquid formulation is desired the tetrapotassium pyrophosphate may vary from about 13 to about 24.5 weight percent, the silica from about 1.4 to about 1.9 weight percent, the sodium alkyl aryl sulfonate from about 14 to about 20 weight percent, the carboxymethylcellulose from about 0.1 to about 3 percent, the mixture of lauryl and myristyl esters from about 4.3 to about 8.2 percent with water making up the balance of the formulation.

When'a paste is desired the formulation may contain from about 25.2 to 30 percent by weight tetrapotassium pyrophosphate, from about 1.9 to about 2.3 percent by weight silica, from about 20 percent to about 23.6 percent by weight sodium alkyl aryl sulfonate, from about 0.1 to about 3 percent carboxymethylcellulose, from about 8.4 to about percent by weight of a mixture of lauryl and myristyl esters and with water making up the balance of the formulation.

In the above compositions, the tetrapotassium pyrophosphate is employed as a phosphate builder while the silicate acts as an anti-corrosion agent. The sodium alkyl aryl sulfonate is employed as a surfactant, the carboxymethylcellulose as an antiredeposition agent and the mixture of lauryl and myristyl esters as a dispersing agent.

The sodium alkyl aryl sulfonate employed as a surfactant is preferably the product marketed by the Atlantic Refining Company under the trade name Ultrawet 35 K, while the carboxymethylcellulose is preferably the product marketed by Hercules Powder under the trade name Hercules CMC 70, and the mixture of lauryl and myristyl esters is preferably the product produced by Synthetic Chemicals, Inc. under the trade name Janusol. Janusol is a proprietary product, whose ingredients are described in US. Patent No. 2,388,281 as sulfated monoestcrs of fatty acids containing at least six carbon atoms and an aliphatic amino alcohol, said ester containing a primary unsubstituted amino group in which the carbon atom binding the amino group is bound to at least two other carbon atoms.

The proportions of the ingredients comprising the formulations of this invention are critical. Small deviations from the recommended contents can cause adverse effects. For example, if the tetrapotassium pyrophosphate content is maintained at about 20 percent by weight, the content of the surfactant may be varied between about 14 and 23.6 weight percent. As the amount of surfactant increases the tetrapotassium pyrophosphate can be increased if the amount of the dispersing agent is also varied so that the ratio of tetrapotassium pyrophosphate to dispersing agent remains at approximately 3 to 1.

In order to obtain the desired product, the procedure which will be described below should be followed. Deviation from this procedure may result in undesirable products.

According to this procedure the dispersant, the mixture of lauryl and myristyl esters, is first dissolved in water. To this solution the tetrapotassium pyrophosphate is added. The addition of the tetrapotassium pyrophosphate to the dispersant gives rise to an emulsion. Immediately after the tetrapotassium pyrophosphate is mixed with the dispersant, the carboxymethylcellulose should be added. This allows advantage to be taken of the heat of solution of the tetrapotassium pyrophosphate and promotes the dispersion and solution of the carboxymethylcellulose. When a uniform slurry has been obtained, the sodium alliyl aryl sulfonate is slowly added and mixed into the formulation. The silicate is added last and this is the most critical step in the preparation since the silicate must be added slowly and with vigorous agitation to prevent gelation. It has been found that mixing is best accomplished with a high-speed mixer, similar in action to the Eppenbach Homo-Mixer. This type of mixture allows for mixing without the entrainment of air. Usually the presence of entrained air causes the dispersion to be unstable.

The following examples are illustrative of the procedure for the formulations of the compositions of this invention and are also illustrative of the formulations themselves. In the examples all the percents are by weight.

Example 1 The following example demonstrates a preferred method of formulation. The formulation used to demonstrate the preparative technique is one which has been Sodium carboxymethylcellulose 0.3 Lauric diethanolamide 2 Mixture of lauryl and myristyl esters 6.7 Water 50 The mixture of lauryl and myristyl esters is made up by esterifying a coconut fatty acid which is composed of about 60% lauryl and myristyl acids and minor amounts of higher fatty acids, with 2-amino-2-methyl- 1,3-propanediol and sulfating the uncombined hydroxy group of the ester.

The mixture of lauryl and myristyl esters is added to at least 20 parts of water at about 25 C. After it has been dissolved with agitation, the tetrapotassium pyrophosphate is added. The resulting mixture is an emulsion that must be agitated to retain its uniformity. Next the carboxymethylcellulose is added with good and continuing agitation to take advantage of the heat of solution of the pyrophosphate. After complete dispersion of the carboxymethylcellulose, the sodium dodecylbenzene sulfonate is dissolved in the remaining 30 parts or less of water. The sodium dodecylbenzene sulfonate is added slowly and with continuous agitation. The lauric diethanolamide is blended in next. The last component added is the silicate. When a liquid silicate is employed, as in this example, care must be taken to add it slowly and with continuous agitation in order to prevent the occurrence of gelation.

The mixing of the formulation in the order described is best accomplished with a high-speed mixer. The product resulting from the preparative technique described above, when stored at about 25 C. does not show evidence of sediment formation or the formation of. multiphases for at least a year.

Example 2 The detergent of Example 1 is prepared by the following procedure. The tetrapotassium pyrophosphate is added at about 25 C. to 50 parts of water with good agitation. After it is dissolved, the silicate is added and blended with the phosphate solution. The sodium dodecylbenzene sulfonate is added next with constant agitation. The lauric diethanolamide is added after the surfactant is blended into the mixture. The mixture of lauryl and myristyl esters is added next. The mixture is now a gummy viscous material which must be warmed to about 60 C. to thin it down to a free-flowing state. Agitation is continued so that the product may be uniform. At the elevated temperature, the sodium carboxymethylcellulose is added and dispersed. When the product is cooled to about 25 C. a gummy gelatinous material settles out of the product within a short period of time. Within several hours the dispersed phase starts to break into a clear and a disperse layer. This product cannot be reconstituted as a stable dispersion type liquid detergent with additional heating and/ or agitation. This procedure illustrates a poor method of formulation.

The following series of examples demonstrate the criticality of the various components on the formation of a,

stable product.

Examples 3-10 Exam les Component p 3 4 6 7 s 9 5a 5b Tetrapotassium Pyrophosphatc. percent... 20 20 20 20 2 20 Sodium Silicate (1:1 Si0;:NazO), percent 2. 90 4.63 0 20 20 20 Sodium Silicate (3.22:1 slopnazo per cent 5 7.9 5 5 5 5 Sodium Dodecylbenzene Sulionate (90%),

percent 15.75 15. 75 15.75 15.75 15.75 15. 75 15. 75 15.75 15. 75 15.75 Lauric Diethanolamide, percent 2 2 2 2 2 2 Laurie Monoisopropanolamide, percent. .1 2 Sodium Carboxyrnethylcellulose, percen .3 3 3 3 3 .3 3. 3 .3 gispfisant, percent. 6. 7 6.7 6. 7 I 6. 7 6. 7 6. 7 6. 7 6. 7 4. 7 9. 7

rig encr, ye percen .1 .1 .1 .1 Water, percent 55. 5 5 .35 50.25 50. 52 47.25 57.55 50.15 47. 45 52.25 48.

Th formulations listed in the above examples are mercially available, solid, spraydried detergent having prepared by the technique illustrated in Example These the following approximate composition: examples demonstrate that silicates with an S1O :Na O

u ratio of 1:1 to 3.22:1 can be employed, that such minor 20 222 2 21 $5 223: a gg 3 components as optical brighten rs and dy s may e in- Anionic Surfactant j 22'85 'corporated in the formulation and the ratio in which the Sodium Carbox meth 1C b tetrapotassium pyrophosphate to dispersant can be em- Sodium sulfafey y ployed. In this connection it should be noted that formu- Water erfume and other minor in ts 6 7 lations 5a and 5b are unstable since they are outside 25 p g 1 n the ratio of tetrapotassium pyrophosphate to dispersant of about 3 to 1.

Examples 1 1-1 9 In the following table the numbers represent the increase in reflectance of the soiled fabrics during the single Examples Component Tetrapotassium Pyrophosphate percent 13 13 13 11.5 22 25 22 11.5 Sodium Silicate (3.22:1 S102: 3.20; 37.6% Solids),

percent 5. 25 5. 25 5. 25 5. 25 5. 25 5. 25 5. 25 5. 25 5. 25 Sodium Dodecylbenzene Sulfonate (90%), percent.-- 13. 1 14 23.6 23.6 14 14 14 23. 6 23.6 Sodium Carboxymethylcellulose, percent 3 3 .3 3 .3 .3 .3 Laurie Diethanolamide, percent 2 2 2 2 2 2 2 2 2 Dispersant,perccnt 4.33 4.33 4.33 10 3.84 7.35 8.34 7.35 3.84 Water, percent (to balance). H I

The formulations listed in Examples 11-19 are pre-' wash. Each number represents the average of 6 reflectpared by the technique in Example 1. The formulations ance readings made on 3 replicate fabric samples: of Examples 11, 15, 17 and 19 are unstable. Example 11 shows the criticality of the sodium dodecylbenzene Water Detergent Spray sulfonate, Examples 15 and 19 show the crrticality of Type ofFabrlc Hardness, g 191 Q i t the pyrophosphate and dispersant. Example 17 shows p eergen the criticality of the tetrapotassium pyrophosphate content at the minimum surfactant content. 0 124 The detergents of this invention are all-purpose deg6 tergents and are useful for laundering cotton, woolen 21 1 goods and fine fabrics, for cleaning hard surfaces, for

other wetting and detergent applications such as wetting and emulsifying agents for insecticides.

Example 20 The detergent properties of the built liquid dispersion detergent of Example 1 are tested by techniques similar to those described in the manual Detergency Evaluation and Testing by J. C. Harris (Interscience Publishers, Inc., 1954). A single wash technique is carried out in a Launder-Ometer (Atlas Electric Devices Co.) at 140 F., using two commercially soiled cotton fabrics (Foster D. Snell Cotton 159 and American Conditioning House 115) in distilled Water, and three commercially soiled cotton fabrics (Foster D. Snell Cotton 159, American Conditioning House 115, and American Conditioning House 130) in 21 g.p.g. synthetic hard Water. A redeposition test is carried out in the Launder-Ometer, using bleached, desized Indian Head cotton fabric and a 0.0025% suspension of carbon black in 0, 6, 12, and 18 g.p.g. synthetic hard water at 140 F. Concentration of the built liquid dispersion detergent in the tests is 0.50%, equivalent to 0.24% solids. Duplicate tests are run simultaneously with a 0.20% solution of a com- Water Hardness, g.p.g. Detergent of Spray Dried Example 1 Detergent These, data show the excellent detergent properties of the built liquid dispersion detergent of this invention.

We claim: I v

1. A creamy high-foam dispersion type detergent composition consisting essentially of from about 13 percent to about 30 percent by weight of tetrapotassium pyrophosphate, from about 1.4 to about 2.3 percent by weight of Si0 as sodium silicate in which the ratio. of SiO /Na O may vary from about 3.2/1 to aboutlzl, from about 14 to about 23.6 percent by weight of sodium dodecyl benzene sulfonate, from about 0.1 to 3 percent by weight of sodium carboxymethylcellulose, from about 4.3 to about 10 percent by weight of a mixture of sulfated monoesters of lauryl and myristyl acids and 2-amino-2- methyl-l,3,-propanediol water comprising the balance of the composition, the ratio of tetrapotassium pyrophosphate to the mixture of lauryl and myristyl esters being approximately 3 to 1.

2. A creamy stable liquid built detergent composition consisting essentially of from about 13 to about 24.5 weight percent of tetrapotassium pyrophosphate, from about 1.4 to about 1.9 percent by weight of SiO as sodium silicate in which the ratio of SiO /Na O may vary from about 3.2/1 to about 1:1, from about 14 to about 20 percent by weight of sodium dodecyl benzene sulfonate, from about 0.1 to about 3 percent by weight of sodium carboxymethylcellulose, from about 4.3 percent to about 8.2 percent by Weight of a mixture of sulfated monoesters of lauryl and myristyl acids and 2-amino-2-methyl-1,3,- propanediol, with water making up the balance of the composition, said tetrapotassium pyrophosphate being in a ratio of approximately 3 to l to the mixture of lauryl and myristyl esters.

3. A stable creamy paste built detergent composition consisting essentially of from about 25.2 to about 30 percent by weight of tetrapotassium pyrophosphate, from about 1.9 to about 2.3 percent by weight of SiO as sodium silicate in which the ratio of SiO /Na O may vary from about 3.2/1 to about 1:1, from about 20 to about 23.6 percent by weight of sodium dodecyl benzene sulfonate, from about 0.1 to about 3 percent by weight of sodium carboxymethylceilulose, from about 8.4 to about 10 percent by weight of a mixture of sulfated monoesters of lauryl and myristyl acids and 2-amino-2- me'thyl-1,3,-propanediol, with water making up the balance of the composition, said tetrapotassium pyrophosphate being in a ratio of about 3 to 1 to the mixture of lauryl and myristyl esters.

4. A stable creamy liquid built detergent composition consisting essentially of about 20 percent by weight of tetrapotassium pyrophosphate, about 5.2 percent by weight of a liquid solution of sodium silicate containing 37.6% solids in which the ratio of S0,, to Na O is about 3.2 to 1, about 15.7 percent by weight of sodium dodecylbenzene sulfonate, about 0.3 percent by Weight of sodium carboxymethylcellulose, about 6.7 percent by weight of a mixture of sulfated monoesters of lauryl and myristyl acids and 2-amino-2-mcthyl-1,3,-propanediol, with water making up the balance of composition.

5. A stable creamy liquid built detergent composition according to claim 4 wherein about 2 percent lauric diethanoiamide is incorporated.

6. A method of preparing a stable, high-foaming built detergent composition which consists essentially of dissolving 4.3 to 10 weight percent of a mixture of sulfated monoesters of lauryl and myristyl acids and Z-amino-Z- methyl-1,3,-propanediol in water, adding to said solution 13 to 30 weight percent of tetrapotassium pyrophosphate to form an emulsion, said tetrapotassium pyrophosphate being in the ratio of about 3 to 1 to the mixture of lauryl and myristyl esters, immediately upon the formation of said emulsion adding 0.1 to 3 weight percent of sodium carboxymethyl cellulose with agitation, upon the formation of a uniform slurry of said components slowly adding 14 to 20 weight percent of sodium dodecyl benzene with agitation, and finally slowly adding 1.4 to 1.9 percent by weight of Si0 as sodium silicate to said mixture with vigorous agitation to prevent gelation.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Chemical Trade Names and Commercial Synonyms, by Haynes, 2nd Ed. (1955), page 232. 

1. A CREAMY HIGH-FOAM DISPERSION TYPE DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 13 PECENT TO ABOUT 30 PERCENT BY WEIGHT OF TETRAPOTASSIUM PYROPHOSPHATE, FROM ABOUT 1.4 TO ABOUT 2.3 PERCENT BY WEIGHT OF SIO2 AS SODIUM SILICATE IN WHICH THE RATIO OF SIO2/NA2O MA VARY FROM ABOUT 3.2/1 TO ABOUT 1:1, FROM ABOUT 14 TO ABOUT 23.6 PERCENT BY WEIGHT OF SODIUM DODECYL BENZENE SULFONATE, FROM ABOUT 0.1 TO 3 PERCENT BY WEIGHT OF SODIUM CARBOXYMETHYLCELLULOSE, FROM ABOUT 4.3 TO ABOUT 10 PERCENT BY WEIGHT OF A MIXTURE OF SULFATED MONOESTERS OF LAURYL AND MYRISTYL ACIDS AND 2-AMINO-2METHYL-1,3,-PROPANEDIOL WATER COMPRISING THE BLANCE OF THE COMPOSITION, THE RATIO OF TETRAPOTASSIUM PYROPHOSPHATE TO THE MIXTURE OF LAURY AND MYRISTYL ESTERS BEING APPROXIMATELY 3 TO
 1. 